The invention relates to additive concentrates, gasoline compositions containing additive concentrates, the preparation of gasoline compositions, and the operation of spark-ignition internal combustion engines.
EP-A-534551 provides a gasoline composition comprising a major amount of a gasoline and from 5 ppmw to 1,000 ppmw based on the gasoline composition of a mixture of (a) an oil soluble polyamine selected from the group consisting of (i) an aliphatic alkylene polyamine containing at least one olefinic polymer chain attached to a nitrogen atom and/or a carbon atom of the alkylene radical(s) connecting the amino nitrogen atoms and said polyamine having a number average molecular weight in the range from 600 to 10,000, (ii) a Mannich polyamine comprising the condensation product of a high molecular weight sulphur-free alkyl-substituted hydroxyaromatic compound wherein the or each alkyl group has a number average molecular weight in the range from 600 to 10,000, an amine which contains an amino group having at least one active hydrogen atom, and an aldehyde, wherein the respective molar ratio of reactants is 1:0.1-10:0.1-10, and (iii) mixtures of (i) and (ii); and (b) an oil soluble hydrocarbyl poly(oxyalkylene) aminocarbamate having a number average molecular weight in the range from 600 to 10,000 having at least one basic nitrogen atom wherein said hydrocarbyl group contains from 1 to 30 carbon atoms, and wherein the weight ratio of said polyamine (a) to said hydrocarbyl poly(oxyalkylene) aminocarbamate (b) ranges from 3:1 to 1:2.
The aliphatic alkylene polyamines of type (a)(i) necessarily contain at least two amino nitrogen atoms. The general formula (I) for preferred polyamines as given on page 3, provides for the polyamine to be a diamine when x in the formula is zero. Exemplified in EP-A-534551 is a composition comprising an N-polyisobutenyl-Nxe2x80x2-Nxe2x80x2-dimethyl-1,3-diamino propane having a molecular weight of 1050 (Mn). There is no mention whatsoever in EP-A-534551 of an aliphatic alkylene additive of type(a)(i) having just one amino nitrogen atom.
WO91/12303 describes a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and about 400 to 1,200 parts per million of a fuel additive composition comprising:
a) a dispersant comprising a hydrocarbyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen atom and an average molecular weight of about 1,000 to about 3,000;
b) an injector detergent comprising a branched chain hydrocarbyl amine having at least one basic nitrogen atom and an average molecular weight of about 300 to about 700, wherein the hydrocarbyl moiety is derived from polymers of C2 to C6 olefins;
c) a fuel demulsifier which is homogeneous with the other components of said fuel additive composition; and
d) a natural or synthetic carrier fluid.
It is said that the fuel additive compositions will in general contain about 10 to 70 weight percent amino carbamate dispersant, about 1 to 10 weight percent of the hydrocarbyl amine injector detergent, about 0.5 to 5 weight percent of the fuel demulsifier and about 25 to 80 weight percent of the carrier fluid (page 12 lines 21 to 26).
On page 18, at lines 6 to 8, of WO 91/12303 it is indicated that the branched chain hydrocarbyl amine having an average molecular weight of about 300 to 700, will in general contain from about 20 to 40 carbon atoms, which corresponds to a molecular weight range from about 280 to about 560.
The molecular weight range of the branched chain hydrocarbyl amines is described as being narrow and peaked near the indicated molecular weight (page 18, lines 12-14). From this it can be deduced that the term xe2x80x9cmolecular weightxe2x80x9d as used in WO 91/12303 means number average molecular weight (Mn)
While the amino component of the branched chain hydrocarbyl amines may be either a monoamine or a polyamine, and this component embodies a broad class of amines having from 1 to 10 amine nitrogen atoms and from 2 to 40 carbon atoms and with a carbon to nitrogen ratio of between about 1:1 and 10:1 (page 18, lines 16 to 12), it is specifically stated that a particularly preferred branched-chain hydrocarbyl amine is polyisobutylene diamine (page 19, lines 1 and 2).
Indeed the only hydrocarbyl amine injector detergent used in the working examples of WO 91/12303 is a polyisobutylene ethylene diamine prepared by the stepwise reaction of a C30 polyisobutylene having a molecular weight of approximately 420 with chlorine and ethylene diamine (page 23, lines 21 to 27).
The favourable effect of using this hydrocarbyl amine injector detergent is demonstrated in Example 9, wherein a fuel additive composition containing this hydrocarbyl amine injector detergent is shown to contribute to the octane requirement of a gasoline composition significantly less than an additive composition comprising an additive package containing a heavy polybutene ethylene diamine made from a polybutene containing on average 100 carbons per molecule and having an average molecular weight of about 1450.
From the teaching of WO 91/12303 the person skilled in the art would be led to conclude that if an injector detergent is to be used in combination with a hydrocarbyl poly(oxyalkylene) aminocarbamate, it should have a relatively low molecular weight below about 700, and preferably about 420, and that it should desirably be a polyamine.
One important property for an additive concentrate to possess is storage stability over a broad range of temperatures, e.g. temperatures as low as xe2x88x9220xc2x0 C. and as high as 40xc2x0 C.
It has now surprisingly been found possible to prepare an additive concentrate containing an hydrocarbyl poly(oxyalkylene) aminocarbamate together with a relatively high molecular weight monoamine, resulting in advantageous storage stability characteristics when compared with similar concentrates based on hydrocarbyl polyamines (e.g. a concentrate corresponding to those in EP-A-534551)
Accordingly, the present invention provides an additive concentrate which comprises an oil soluble hydrocarbyl poly(oxyalkylene) aminocarbamate having a number average molecular weight (Mn) in the range 600 to 10,000 having at least one basic nitrogen atom wherein said hydrocarbyl group contains 1-30 carbon atoms, and an oil soluble hydrocarbyl amine of formula Rxe2x80x94NH2 wherein R represents a group Rxe2x80x2 or a group Rxe2x80x2xe2x80x94CH2xe2x80x94, wherein Rxe2x80x2 represents a hydrocarbyl group having a number average molecular weight (Mn) in the range 750 to 6,000.
In the description which follows, all molecular weight values are number average molecular weights (Mn), unless otherwise indicated.
As described in EP-A-534551, the amine component of the oil soluble hydrocarbyl-terminated poly(oxyalkylene) aminocarbamate is preferably derived from a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms. The polyamine is preferably reacted with a hydrocarbyl poly(oxyalkylene) chloroformate to produce the hydrocarbyl poly(oxyalkylene) aminocarbamate component. The chloroformate is itself derived from hydrocarbyl poly(oxyalkylene) alcohol by reaction with phosgene. The polymer, encompassing diamines, provides the product poly(oxyalkylene) aminocarbamate with, on average, at least one basic nitrogen atom per carbamate molecule, i.e., a nitrogen atom titratable by strong acid. The polyamine preferably has a carbon-to-nitrogen ratio in the range from 1:1 to 10:1. The polyamine may be substituted with substituents selected from hydrocarbyl groups having from 1 to 10 carbon atoms, acyl groups having from 2 to 10 carbon atoms, and monoketone, monohydroxy, mononitro, monocyano, alkyl and alkoxy derivatives of hydrocarbyl groups having from 1 to 10 carbon atoms. It is preferred that at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen. Examples of suitable polyamines are those described in U.S. Pat. No. 4,191,537.
Hydrocarbyl, as used in describing all the components of this invention, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combination thereof, e.g., aralkyl. Preferably, the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation. The more preferred polyamine for the aminocarbamate component is a polyalkylene polyamine, including alkylenediamine, and including substituted polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine.
Preferably, the alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms. Examples of such polyamines include ethylenediamine, diethylene triamine, triethylene tetramine, dipropylene triamine, tetraethylene pentamine and pentaethylene hexamine. Among the polyalkylene polyamines, polyethylene polyamines and polypropylene polyamines containing 2-12 amine nitrogen atoms and 2-24 carbon atoms, are especially preferred, with the lower polyethylene/polypropylene polyamines, e.g. ethylenediamine and dipropylene triamine, being most preferred.
The hydrocarbyl-terminated poly(oxyalkylene) polymers which are utilised in preparing the aminocarbamates are monohydroxy compounds, e.g., alcohols, often termed monohydroxy polyethers, or polyalkylene glycol monocarbyl ethers, or xe2x80x9ccappedxe2x80x9d poly(oxyalkylene) glycols, and are to be distinguished from the poly(oxyalkylene) glycols (diols), or polyols, which are not hydrocarbyl-terminated, i.e., are not capped. The hydrocarbyl-terminated poly(oxyalkylene) alcohols are produced by the addition of lower alkylene oxides, such as ethylene oxide, propylene oxide and butylene oxide to the hydroxy compound ROH under polymerisation conditions, wherein R is the hydrocarbyl group which caps the poly(oxyalkylene) chain. In the poly(oxyalkylene) component of the aminocarbamate, the group R will contain from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms and is aliphatic or aromatic, i.e. an alkyl or alkylphenyl wherein the alkyl is a straight or branched-chain of from 1 to 24 carbon atoms. The oxyalkylene units in the poly(oxyalkylene) component preferably contain from 2 to 5 carbon atoms but one or more units of a larger carbon number may also be present. Each poly(oxyalkylene) polymer contains at least 5 oxyalkylene units, preferably 8 to 100 oxyalkylene units, more preferably 10 to 100 units and most preferably 10 to 25 such units. The poly(oxyalkylene) component is more fully described and exemplified in U.S. Pat. Nos. 4,191,537 and 4,197,409. The hydrocarbyl poly(oxyalkylene) aminocarbamate used in the compositions of the present invention is obtained by linking the amine component and the poly(oxyalkylene) component together through a carbamate linkage, i.e.,
xe2x80x94Oxe2x80x94C(O)xe2x80x94Nxe2x80x94
wherein the oxygen may be regarded as the terminal hydroxyl oxygen of the poly(oxyalkylene) alcohol component, and the carbonyl group, xe2x80x94C(O)xe2x80x94, is preferably provided by a coupling agent, e.g., phosgene. In the preferred method of preparation the hydroxycarbyl poly(oxyalkylene) alcohol is reacted with phosgene to produce a chloroformate and the chloroformate is reacted with the polyamine. The carbamate linkages are formed as the poly(oxyalkylene) chains are bound to the nitrogen of the polyamine through the oxycarbonyl group of the chloroformate. Since there may be more than one nitrogen atom of the polyamine which is capable of reacting with the chloroformate, the aminocarbamate contains at least one hydrocarbyl poly(oxyalkylene) polymer chain bonded through an oxycarbonyl group to a nitrogen atom of the polyamine, but the carbamate may contain 1, 2 or more such chains. It is preferred that the hydrocarbyl poly(oxyalkylene) aminocarbamate product contains, on average, 1 poly(oxyalkylene) chain per molecule (i.e., is a monocarbamate), although it is understood that this reaction route may lead to mixtures containing appreciable amounts of di- or higher poly(oxyalkylene) chain substitution on a polyamine containing several reactive nitrogen atoms. Several especially preferred aminocarbamates are butyl-poly(oxyalkylene)-N-(2-aminoethyl) carbamate and alkyphenyl-poly(oxyalkylene)-N-(2-aminoethyl) carbamate. A particularly preferred to carbamate can be expressed by the following formula: 
wherein R is a hydrogen atom or an alkyl group and m is greater than 5. Aminocarbamates suitable for use in the present invention can be obtained from the Oronite Additives Division of Chevron Chemical Company.
Synthetic methods to avoid higher degrees of substitution, methods of preparation, and other characteristics of the aminocarbamates used in the present invention are more fully described and exemplified in U.S. Pat. Nos. 4,191,537 and 4,197,409.
The number average molecular weight of the aminocarbamate will range from 600 to 10,000 (Mn), preferably from 600 to 5,000 (Mn) and most preferably from 600 to 2,000 (Mn)
In the oil soluble hydrocarbyl amine of formula Rxe2x80x94NH2, wherein R represents a group Rxe2x80x2 or a group Rxe2x80x2xe2x80x94CH2xe2x80x94, Rxe2x80x2 preferably represents a hydrocarbyl group having a number average molecular weight (Mn) in the range 900 to 3,000, more preferably in the range 950 to 2,000, and most preferably in the range 950 to 1,350. Hydrocarbyl amines wherein Rxe2x80x2 represents a hydrocarbyl group having a number average molecular weight (Mn) in the range 950 to 1,050 have been found to be very effective in the present invention.
The number average molecular weight, (Mn), of hydrocarbons, e.g. polyalkenes, may be determined by several techniques which give closely similar results. Conveniently, (Mn) may be determined for example by vapour phase osmometry (VPO) (ASTM D3592) or by modern gel permeation chromatography (GPC), e.g. as described for example in W. W. Yau, J. J. Kirkland and D. D. Bly, xe2x80x9cModern Size Exclusion Liquid Chromatographyxe2x80x9d, John Wiley and Sons, New York, 1979.
Conveniently, the group R may represent a group Rxe2x80x2 or a group Rxe2x80x2xe2x80x94CH2xe2x80x94, wherein Rxe2x80x2 represents a polymeric substituent derived from alkanes or alkenes with straight or branched chains which may or may not have aromatic or cycloaliphatic substituents, for example groups derived from polymers or copolymers of olefins which may or may not have a residual double bond.
Rxe2x80x2 may advantageously represent a polymeric substituent derived from at least one olefinic monomer having from 2 to 6 carbon atoms. Preferred polymeric substituents are polyalkenyl substituents such as polyethenyl-, polypropenyl-, polybutenyl-, and polyisobutenyl-groups.
The hydrocarbyl amine of formula Rxe2x80x94NH2 may be prepared in known manner, e.g. by hydroformylation of a suitable olefin precursor followed by amination under hydrogenating conditions, e.g. in a manner analogous to that described in U.S. Pat. No. 4,832,702. U.S. Pat. No. 4,832,702 specifically discloses the preparation of polybutenyl- and polyisobutenyl amines from an appropriate polybutylene or polyisobutylene by hydroformylation and subsequent amination of the resulting oxo product under hydrogenating conditions.
The olefin precursor is preferably a polyolefin e.g. polyethylene, polypropylene, polybutylene or polyisobutylene. Preferred polyolefins are polyisobutylenes prepared from isobutene and up to 20% of n-butene.
The reactivity of a polyolefin depends upon the number and location of the olefinic double bonds in the molecule. Generally, a reactive polyolefin is one in which more than 10% of the double bonds are in an alpha position. While a wide range of polyolefins may suitably be used in the preparation of the hydrocarbyl amines of the present invention, it is preferred that the polyolefin employed is a reactive polyolefin, more preferably a highly reactive polyisobutylene.
The term xe2x80x9chighly reactive polyisobutylenexe2x80x9d has been defined in U.S. Pat. No. 5,916,825 (Column 3, lines 4 to 50). as referring to a polyisobutylene wherein greater than 70% of the residual olefinic double bonds are of the vinylidene type, i.e., represented by the formula: 
Examples of preferred polyisobutylenes are those obtainable from BP Amoco Ltd. under the trade mark xe2x80x9cUltravisxe2x80x9d, and BASF A.G. under the trade mark xe2x80x9cGlissopalxe2x80x9d.
When the hydrocarbyl amine of formula Rxe2x80x94NH2 is prepared by a method analogous to U.S. Pat. No. 4,832,702, R represents a group Rxe2x80x2xe2x80x94CH2xe2x80x94, wherein Rxe2x80x2 preferably represents a polyalkenyl substituent. More preferably, when R represents Rxe2x80x2xe2x80x94CH2xe2x80x94, Rxe2x80x2 represents a polyisobutenyl substituent.
Hydrocarbyl amines especially suitable for use in the additive concentrates of the present invention are obtainable from BASF A.G. under the trade marks xe2x80x9cKeropurxe2x80x9d and xe2x80x9cKerocomxe2x80x9d.
The additive concentrate of the present invention may conveniently be prepared by admixing the oil soluble hydrocarbyl poly(oxyalkylene) aminocarbamate and the hydrocarbyl amine of formula Rxe2x80x94NH2. In the concentrate, the weight ratio of the hydrocarbyl poly(oxyalkylene) aminocarbamate to the hydrocarbyl amine of formula Rxe2x80x94NH2 is preferably in the range 6:1 to 1:6, more preferably in the range 3:1 to 1:3, even more preferably in the range 2:1 to 1:3, and most preferably in the range of 1:1 to 1:3. In an especially preferred additive concentrate the weight ratio is in the range 1:1 to 1:2.
In a preferred embodiment of the present invention, the concentrate may also contain an anti-corrosion agent. Suitable anti-corrosion agents include those commercially sold by Rhein Chemie, Mannheim, Germany as xe2x80x9cRC 4801xe2x80x9d, or a polyhydric alcohol ester of a succinic acid derivative having on at least one of its alpha carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group having from 20 to 500 carbon atoms, for example, pentaerythritol diester of polyisobutylene-substituted succinic acid, the polyisobutylene group having an average molecular weight of about 950.
An anti corrosion additive which may very conveniently be used in the additive concentrate of the present invention can be obtained from REChem A.G., Bern, Switzerland, under the designation xe2x80x9cER27xe2x80x9d.
The additive concentrate of the present invention may also contain other conventional additives including antioxidants such as phenolics, e.g. 2,6-di-tert-butylphenol or phenylenediamines, e.g. N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, dyes, metal deactivators, and dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins.
The additive concentrate of the present invention may further contain an amount of carrier fluid. Suitable carrier fluids, when utilized, include hydrocarbon based materials such as polyisobutylenes (PIB""s), polypropylenes (PP""s) and polyalphaolefins (PAO""s), all of which may be hydrogenated or unhydrogenated but are preferably hydrogenated; polyether based materials such as polybutylene oxides (poly BO""s), polypropylene oxides (poly PO""s), polyhexadecene oxides (poly HO""s) and mixtures thereof (i.e. both (poly BO)+(poly PO) and poly BOxe2x88x92(PO)); and mineral oils such as those sold by member companies of the Royal Dutch/Shell group under the designations xe2x80x9cHVIxe2x80x9d and xe2x80x9cXHVIxe2x80x9d (trade mark), Exxon Naphthenic 900 sus mineral oil and high viscosity index oils in general.
The additive concentrate of the present invention may further contain an amount of diluent.
Suitable diluents are hydrocarbons and mixtures of hydrocarbons with alcohols or ethers, such as methanol, ethanol, propanol, 2-butoxyethanol, methyl tert-butyl ether or higher alcohols such as xe2x80x9cDobanol 91xe2x80x9d (Trade Mark) available from member companies of the Royal Dutch/Shell group.
Preferably the diluent is an aromatic hydrocarbon solvent such as toluene, xylene, mixtures thereof or mixtures of toluene or xylene with an alcohol. Additionally preferred diluents include xe2x80x9cShellsolABxe2x80x9d, xe2x80x9cShellsolRxe2x80x9d, (Trade Marks) and low aromatic white spirit (LAWS), which are available from member companies of the Royal Dutch/Shell group.
It will be recognised that where the additive concentrate of the present invention contains a hydrocarbyl poly(oxyalkylene) aminocarbamate or hydrocarbyl amine component which has been obtained from a commercial supplier, that component may, in addition to the aminocarbamate or amine itself, contain a proportion of diluent and/or carrier fluid. The carrier fluid may take the form of unreacted intermediate from the manufacturing process, for example polyether in the case of the aminocarbamate, or polyisobutylene in the case where the amine is a polyisobutyl amine.
In the additive concentrates and gasoline compositions of the present invention, such proportions of diluent and/or carrier fluid are considered as being a part of the carrier fluid and/or diluent which the additive concentrate and compositions may additionally contain.
In the additive concentrates, the oil soluble hydrocarbyl poly(oxyalkylene) aminocarbamate is preferably present in an amount from 5% to 90% w, more preferably 10% to 60% w and most preferably 20% to 50% w, while the hydrocarbyl amine of formula Rxe2x80x94NH2 is preferably present in an amount from 5% to 95% w, more preferably 15% to 90% w, and most preferably 20% to 80% w, all percentages by weight being based upon the total weight of the concentrate.
When the concentrate additionally contains an anti-corrosion agent it is preferably present in an amount from 0.1% to 10% w, more preferably 0.1 to 5% w.
When the concentrate additionally contains an amount of carrier fluid and/or diluent, the amount of carrier fluid and/or diluent present is preferably in the range from 5 to 80% w, more preferably 10 to 70% w, and most preferably 20 to 60% w, based on the total weight of the concentrate.
The present invention also provides a gasoline composition comprising a major amount of a gasoline suitable for use in spark ignition engines, and a minor amount of additive concentrate according to the present invention. By a major amount of gasoline it is meant that more than 50% w of the composition is gasoline, while by minor amount of additive concentrate it is meant that less than 50% w of the composition is concentrate, the percentages by weight being based upon the total weight of the gasoline composition. Preferably, the minor amount of concentrate comprises less than 10% by weight of the gasoline composition.
In the gasoline composition of the present invention the weight ratio of the hydrocarbyl poly(oxyalkylene) aminocarbamate to the hydrocarbyl amine of formula Rxe2x80x94NH2 is preferably in the range of 6:1 to 1:6, more preferably in the range 3:1 to 1:3, even more preferably in the range 2:1 to 1:3, and most preferably in the range of 1:1 to 1:3.
The amount of hydrocarbyl poly(oxyalkylene) aminocarbamate in the gasoline composition is preferably in the range 25 to 2,500 ppmw (parts per million based on total weight of the fuel composition), more preferably in the range 50 to 1,000 ppmw, even more preferably in the range 50 to 500 ppmw and most preferably in the range 50 to 250 ppmw, based on total composition. The amount of hydrocarbyl amine of formula Rxe2x80x94NH2 in the gasoline composition is preferably in the range 25 to 2,500 ppmw, more preferably in the range 50 to 1,000 ppmw, even more preferably in the range 50 to 500 ppmw, and most preferably in the range 50 to 250 ppmw, based on total composition.
The hydrocarbyl poly(oxyalkylene) aminocarbamate and the hydrocarbyl amine of formula Rxe2x80x94NH2 are preferably present in the gasoline composition in a combined amount in the range of 50 to 5,000 ppmw, more preferably 100 to 1,000 ppmw and most preferably 100 to 500 ppmw, based on total composition.
When the gasoline compositions of the present invention additionally contain an anti-corrosion additive it is preferably present in an amount from 1 to 1,000 ppmw, more preferably 1 to 500 ppmw and most preferably 1 to 50 ppmw.
When the gasoline compositions additionally contain an amount of carrier fluid and/or diluent, the amount of carrier fluid and/or diluent present is preferably in the range from 50 to 5,000 ppmw, more preferably 100 to 1,000 ppmw, and most preferably 100 to 500 ppmw, based on total composition.
Typical gasolines suitable for use in spark ignition engines are mixtures of hydrocarbons having a boiling point in the range from 25xc2x0 C. to 232xc2x0 C. and comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferred are gasoline blends having a saturated hydrocarbon content ranging from 40 to 80 percent volume, an olefinic hydrocarbon content ranging from 0 to 30 percent volume and an aromatic hydrocarbon content ranging from 10 to 60 percent volume. The base fuel can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer or trimerised olefins, synthetically produced aromatic hydrocarbon mixtures from thermally or catalytically reformed hydrocarbons, or from catalytically cracked or thermally cracked petroleum stocks, or mixtures of these. The hydrocarbon composition and octane level of the base fuel are not critical. The octane level, (R+M)/2, will generally be above 85. Any conventional base gasoline may be employed in the practice of this invention. For example, in the gasoline, hydrocarbons can be replaced by up to substantial amounts of conventional alcohols, or ethers, conventionally known for use in fuels. Alternatively, e.g. in countries such as Brazil, the xe2x80x9cgasolinexe2x80x9d may consist substantially of ethanol.
Preferably, the gasolines used in the present invention are lead-free, but can contain minor amounts of blending agents such as methanol, ethanol and methyl tertiary butyl ether e.g., from 0.1 to 15% volume of the base fuel. The gasolines themselves can also contain antioxidants such as phenolics, e.g., 2,6-di-tert-butylphenol or phenylenediamines, e.g., N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, dyes, corrosion inhibitors, metal deactivators and dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins. The gasolines may also contain antiknock compounds such as a methyl cyclopentadienylmanganese tricarbonyl and ortho-azidophenol as well as co-antiknock compounds such as benzoylacetone. Although the gasolines are preferably lead-free, gasolines containing tetraethyl lead or other lead-containing compounds, can be employed where permitted by law.
The present invention further provides a process for the preparation of a gasoline composition which comprises adding an additive concentrate according to the invention to a gasoline. The present invention further provides a method of operating a spark-ignition internal combustion engine which comprises introducing into the combustion chambers of said engine a gasoline composition according to the present invention.
The invention will be further understood from the following illustrative examples. In the examples the various additives are designated as follows:
(a) xe2x80x9cOGA 480xe2x80x9d contains a hydrocarbyl poly(oxyalkylene) aminocarbamate (Mn=1,400 to 1,800) and hydrocarbon solvent, approximately 50% w/w being volatile material. OGA 480 is obtainable from the Oronite Additives division of the Chevron Chemical Company. xe2x80x9cOGA 499xe2x80x9d, obtainable from the same source as xe2x80x9cOGA 480xe2x80x9d is understood to contain essentially the same hydrocarbyl poly (oxyalkylene) aminocarbamate.
(b) xe2x80x9cPIBAxe2x80x9d is polyisobutylene monoamine (PIB-CH2xe2x80x94NH2), in which the polyisobutylene (PIB) chain has a number average molecular weight (Mn) of approximately 1,000, in the form of an approximately 50% w/w solution in hydrocarbon solvent of PIB-CH2xe2x80x94NH2. PIBA was obtained from BASF A.G. under the trade mark xe2x80x9cKerocomxe2x80x9d.
(c) xe2x80x9cPIB-EDAxe2x80x9d is a polyisobutylene ethylenediamine (N-polyisobutenyl-1,2-diaminoethane), in which the polyisobutylene chain has a number average molecular weight (Mn) of approximately 1,000, in the form of an approximately 55% w/w solution in xylene of polyisobutylene ethylenediamine.
(d) xe2x80x9cPIB-DAPxe2x80x9d is N-polyisobutenyl-Nxe2x80x2-Nxe2x80x2-dimethyl-1,3-diaminopropane, in which the polyisobutylene chain has a number average molecular weight (Mn) of approximately 1,000, in the form of an approximately 55% w/w solution in xylene of N-polyisobutenyl-Nxe2x80x2-Nxe2x80x2-dimethyl-1,3-diaminopropane.